Trisazo dyestuffs



Patented Nov. 17, 1953 UNITED STATES TRISAZO DYESTUFFS Werner Bossard, Riehen, near Basel, and Otto Bitterlin, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm' No Drawing. Application November 29, '1951',

1 Serial No. 258,993. J

I Claims priority, application Switierl'and December 15, 1950 6 Claims. (01. 260-472) The present process concerns the production of substantive trisazo dyestuffs which are characterised by their good drawing power on to cellulose fibres from a bath containing Glaubers salt, by the pure shades of their direct cellulose dyeings and the excellent fastness to water thereof and by their very good dischargeability.

It is not sufficient for the production of white or multi-coloured discharges that the dyeing which serves as a base is pure uhite dischargeable; in addition it must have very good fastness to water so that the dyestufi does not run from the dyed to the discharged places when the cleavage products are washed out. Up to now, generally only after-treated dyeings have been able to be used for discharge articles which with suitable composition of the used azo dyestufi are made insoluble and sufficiently fast to water either by diazotisation on thefibre and coupling.

with the azo components having no groups making them soluble (diazotisation dyestuffs), or by coupling on the fibre with diazo compounds having no groups rendering them soluble (development dyestuffs), or by after-treatment with formaldehyde (formal dyestuffs), or metallising on the fibre. In contrast to these types of dyestufis, azo dyestuffs, the direct cellulose dyeings of which can be discharged without any aftertreatment, are much more easy to apply and therefore are more advantageous from the point of view of materials and time required. They are, therefore, very highly valued. The present invention enables such dyestuffs usable for the direct dyeing of discharge articles to be prepared.

The trisazo dyestuffs according to the invention are obtained by coupling diazomonoazo com pounds of the general formula I:

e A-N=NBXGN=N wherein X represents a member selected from the group consisting of the diphenyl linkage, the CO"NH-'-- and NI-ICO-radicals, A represents an unsulfonated radical of the benzene series containing a carboxyl group in the m-position and a hydroxyl group in the p-position to the-N=N group, B and C represent an unsulfonated radical of the benzene series, with 2-(4-aminobenzoylamino) hydroxynaphthalene 'I-sulfonic acids, further diazotising the disazo dyestufi so obtained and coupling with 1 mol of 1.3-dihydroxybenzene'as end component.

The diazomonoazo'compounds usable according to the invention are obtained according to various methods all of which are known per se, erg. by tetrazotisation of 4.4-diaminodiphenyl-" or of 4-(4'-aminobenzolyamino)-1-aminobenzene compounds and unilateral coupling with an o-hydroxycarboxylic acid of the benzene series coupled in the para position to the hydroxyl 5 group. Also the 4' amino-4-hydroxy-3 carboxyazobenzene compounds obtained by methods known per se can be acylated with 4-nitrobenzoyl halides, the nitro group converted into the primaryv amino groupbyhnown methods, e. g.

10 with sodium sulfide and the aminoazo dystuffj' so 'obtained diazotised.-- Alkyl, in particular, methyl groups can be named as possible substituents of the radicals l3 and C, while apart from salicyclic acid, the homologuescf thiscompound coupled in the para position to the hydroxyl group come into consideration as starting components. Chiefiy 2-(4'-aminobenzoylamino)-5- hydroxynaphthalene-7-sulfonic acid comes into consideration as technically easily accessiblecou-' g0 pling component usable according to the present invention. The coupling with the 2-(4'-aminobenzoylamino; 5 -hydr9; yn aphthalene-{ksulfonic acids ismade in theu'sual wayinaweakly alka line aqueous medium',- .for. .example in the-pres- ;;ence of sodium bicarbonate. The further diazotisation of the amino-disazo dyestuif is done in an aqueous suspension with 'sodium' nitrite and:

mineral acid and the final coupling with 1.3-dihydroxybenzene is performed advantageously in a soda-alkaline aqueous solution. According to the individual composition, the.

trisazo dyestuffs according to the invention dye cellulose fibres in shades from yellowish to scarlet reds and scarlet to wine reds from a dyebath containing Glaubers salt. The dyestuffs accord ing to the invention, the radicals B and C of which contain no other substituents, produce particularly pure shades. Although halogen and methyl groups only slightly cloud the shade, al-

koxy groups do so to a greater extent. The dyestuffs according to the invention having the bridging members -NH CQ. and

are characterised by particularly brilliant shades.

disazo dyestuffs obtained from 4-(4"-aminobenzoylamino) 4- hydroxy-3-carboxy-azobenzene and 2 (4' aminobenzoylamino) 5 hydroxynaphthalene-'I-sulfonic acid can be diazotised on the fibre and can be coupled with the usual de-f veloping agents'to produce trisazo dyestulfs. As,-

however, the water soluc-ility and substantivity of the substantive diazotisation dyestuifs are generally altered fundamentally during development, thecgoodsubstantivity of the trisazo dyestuffs according to the inventicniandthe good fastness to water of their cellulose dyeings was not obvious from the known facts.

The following examples illustrate the invention without limiting it in any way. Part iare given as parts by weight and the temperatures are in degrees centigrade.

Examplet l 18.4 parts of 4.4-diaminodiphenylzareztetrazm tised in the usual way in a hydrochloric acfdasclution with 13.8 parts of sodium nitrite. The tetrazo solution is then coupled alkalinewithl4i3 parts of 2-hydroxybenzene-1-carboxylic acid and then with 35.8 parts of 2(4-aminobenzoylamino) --hydroxynaphthalenefl-sulfonic acid in albicarbcnate. alkaline solution. .Thezdisazo dyestuff which :is .difiicultlyr soluble iis :filtered eoif .at 50 and pasted in .1000 -parts-of waterand 1 .6 parts of-100% caustic-soda lye. After'theadditicn of -7.6'parts of'sodium nitrite, diazotisation is performed by the quick addition of 48 :parts of do on 30% hydrochloricacid-at on completion'of the=diazotisation, the suspension is'poured into an-aqueousrsolution of 11:parts of LS-dihydroxybenZene and-SO parts of soda. Afterthe addition of commonsalt, the itrisazodyestufi of the formula:

' i; cos

is. filtered Fhotand "dried. it? is 2a 'b'rownz'pcwder which dissolves'i'n water'vvithm :red and in concentratedrsulphuric acidWithL'aidaTk bluecolour. The dyestuff dyes :natural .or megenerated cellulose fibres 'in bluishi-red'is'hades which have :'excellent ."fastness to water iand ;canirbe ;discha'rged pure white.

If 21.2 parts of :3;3 edimethyl eiil -iliaminodiphenyl 'areused' instead of 18.4 parts of 4;4' -"diaminodiphenylor'if 15.7 parts'of 3- or l methyl- 2=hydroxybenzene-1-earboxylicf acid are used instead "of 14.3 pa'rts 'of 2-'hydroxyben'z'ene l carboxylic acid and the prccduredescfibe' above is followed, dyestuifs with similar properties are obtained.

Example 2 28.5 parts of the sodium salt of the aminoazo dyestufi produced-in-the usualmanner either by coupling .l-amino-enitrobenzene with l2-hydroxybenzene-l-carboxylic acid and .then reducing 'the-nitro'group; or diazotising 1-acetylamino- I 4-aminobenzene, coupling with -2-hydroxybenzene-l-carboxylic acid and finally saponifying the acetylaminogroup, aredissolved in 220 parts of-water at 70.

22.5 parts of 4-nitrobenzoy1chloride and 6.6 parts of sodaare added. When a sample can'no longer be-diazotised 13:6 --partsofdehydrated :so

4 dium sulphide are added, the temperature is raised to 80 and kept for some time at this temperature after which 120 parts of common salt are .added and the reaction .mixture .is filtered. 5 The aminobenzoylated monoazo dyestuffs so obtained is pasted in 600 parts of water and 5.5 ,-.pa1:ts of 100% caustic soda lye. 7.6 parts of sodium nitrite are added and the whole i added 'idtopwiseiat 35 to 68 parts of conc. hydrochloric ii?- acidand 68 parts of water. On completion of the 'di'a'zotisationithe diazo compound is coupled with .anaqueous solution of 35.8 parts of 2-(4-amino- 'benzoylamino)-5-hydroxynaphtha1ene 7 sullfonic acidinlthe'presence of parts of sodium M'bicaibonate at The disazo dyestufi which is .difiicultly .solubleis filtered oil at 90, washed .ifree .of the accompanying yellow by-products, pasted in 1000 parts of water and 1.6 parts of 106% 'caustic soda lye at 10 and, after the addi- 20tion of 7.6 parts of sodium nitrite, diazotised by thequick (addition of 48 parts .of-% -hydrochloric acid. After 6 hours, the suspension is coupled with 'asolution .ofll parts :of 1;3-dihydroxybenzene and parts of soda. After 24 25 hours, 350parts of common salt are added to the trisazo dyestufl of the following formula:

35 while it'is hotpwhereupon'it is filtered 'ofi and dried. The dyestuff is a red-'brownpowder-which dissolves'witha red colour'both in water and in conc5sulfuric acid. Itdyes cellulose inpure yellowish-red shades which arejremarkablyfast to water and. can be discharged pure-white. If, in

theplacemf :the :28.5"parts 0f the m'onoazo dyestuff from l-amino-4 nitr'obenzene and 2-hydroxybenzene-l-carboxylic acid, 29.8 parts of the .monoazo dyestuif from 4-nitro-2- or -3-methyll-amin'obenzene and 2-hydroxybenzene-1-carboxylica'cid'are used and if instead of Z-hydroxybenzene-i-ca'rboxylic acid, the equivalent number o"i"parts of 3-methyl-2-hydroxybenzene-1- carboXylic acid or 4-nethyl-2-hydroxybenzenel'-carboxylic acid are used for the productionof the monoazo dyestufi and the procedure described above is followed, dyestuifs are obtained which have similar properties.

Example '3 parts of 100% caustic soda lye, 7.6 parts of so-' dium nitrite are added and-the suspension is then added dropwise to 68 parts of 30% hydrochloric acid and 68 parts of water at 35. After a few hours, the diazo compound is coupled at -5 with a. solution of 35.8 parts of 2-(4'-aminobenzoylamino) -5-hydroxynaphthalene 7 sulfonic acid and parts of sodium bicarbonate in 720 parts of water. The next day 150 parts of common salt are added to the disazo dyestuff, it is then filtered off and pasted at 10 in 1000 parts of water and 1.6 parts of caustic soda lye. After the addition of 7.6 parts of sodium nitrite, 48 parts of hydrochloric acid are quickly poured in and after a few hours the diazo compound is coupled to an 000E aqueous solution of 11 parts of 1.3-dihydroxybenzene and 55- parts of soda. The trisazo dyestuff of the formula:

22.? parts of 1-(4'-aminobenzoylamino) -4=- COOH aminobenzene and 13.8 parts of sodium nitrite are tetrazotised at l0-11 in the usual way and then coupled with a solution of 15.2 parts of 2- hydroxybenzene-l-carboxylic acid and parts of soda in 250 parts of water. After the diazomonoazo dyestuff has formed, the suspension HOaS COOH

which has been neutralised with 25 parts of 30% hydrochloric acid is coupled to a solution of .HOaS

O OH

Boss-- 6, 35.8 parts 'of 2-'(4"-aminobenzoylamino) -5-hydroxynaphthalene-7-sulfonic acid in the presence of 45.4 parts of sodium bicarbonate at 40. After 24 hours, the disazo dyestuff which has completely formed is filtered off, stirred into 1000 parts of water and 1.6 parts of 100% caustic soda lye and, at 10, 7.6 parts of sodium nitrite and finally 48 parts of 30% hydrochloric acid are added. On completion of the diazotisation, the suspension is poured into and so coupled with an aqueous solution of 11 parts of 1.3-dihydroxybenzene and 50 parts of soda. The trisazo dyestuff which is diificultly soluble is filtered ofi at 50 and dried.

It has the i rmula;

and is a brown powder. It dissolves in water with a brown-red colour and in concentrated sulfuric acid with a dark red colour. Cellulose fibres are dyed in pure red shades which have excellent water fastness properties. In addition', the dyeings are pure white dischargeable both from a neutral or alkaline medium.

If, in the above example, the 22.? parts of 1- (4 -aminobenzoylamino) -4-aminobenzene are replaced by 24.1 parts of 1-(4-aminobenzoylamino) -d-amino-2-methylbenzene or 25.5 parts of 1- (4aminobenzoylamino) 4-amino-2.5-di methylbenzene or the 15.2 parts of Z-hydroxybenzene-l-carboxylic acid are replaced by 16.6 parts of 3- or 4-methyl-2-hydroxybenzene-1- carboxylic acid and the procedure described above is followed, dyestuffs with similar properties are obtained.

What we claim is:

1. A trisazo dyestufi of the general formula:

wherein X represents a member selected from the group consisting of the diphenyl linkage, the CO-NH and NI-I-CO-- radicals, Y1 Y2 and Y3 are selected from the group consisting of hydrogen and lower alkyl groups.

2. A trisazo dyestufi of the formula:

3. A trisazo dyestuff of the formula:

: 5. Atrisazo dyestufiof'the formula:

6. A trisazo dyestufi of the-"formula:

BOSSARD. OTTO BITTERLIN.

References "Cited in the file of this patent UNITED STATES PATENTS Number Name "Date 1,901,393 Glietenberg "Mar. 14, 1933 2,195,089 Kollmann Mar. 26, 1940 2,19(i,028 :Roosv k Apr. 2,1940 

1. A TRISAZO DYESTUFF OF THE GENERAL FORMULA: 